CN105964310B - The preparation method and purposes of anion exchange in-line purification Solid Phase Extraction integral post - Google Patents
The preparation method and purposes of anion exchange in-line purification Solid Phase Extraction integral post Download PDFInfo
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Abstract
A kind of Preparation method and use of anion exchange in-line purification Solid Phase Extraction integral post.The integral post is using dimethylaminoethyl acrylate methyl ammonia ethyl ester as monomer, and methacrylic acid glycol ester is crosslinking agent, and normal propyl alcohol and PEG-400 are pore-foaming agent, and azodiisobutyronitrile is initiator；It pours into stainless steel tube and seals after ultrasonic mixing, degassing, 55 DEG C~65 DEG C of water-bath are reacted 20~30 hours, and poly (DMAEMA-co-EDMA) integral post is obtained.The integral post can be used for the residue detection analysis of acid agrichemical in veterinary antibiotics.The integral post in-situ polymerization is resistant to certain pressure in the chromatographic column of stainless steel, can access in-line purification enrichment system, realizes the automation of Solid phase extraction step.And preparation method is simple, has continuous poriferous structure, it is higher than traditional filling extraction efficiency, column back-pressure is low so that resistance to mass tranfer is obviously reduced convenient for the outflow of mobile phase；And it can reuse.
Description
Technical field
The invention belongs to analytical chemistry fields.More particularly to a kind of anion exchange in-line purification Solid Phase Extraction integral post
The copolyreaction of dimethylaminoethyl acrylate methyl ammonia ethyl ester and ethylene glycol dimethacrylate is used especially in stainless steel chromatographic column
The polyalcohol integral pole of formation, preparation method and application.
Background technique
Integral post is as the Solid Phase Extraction new material in a kind of rapid development, because penetrating pore structure containing special,
So that Monolithic Columns itself have excellent permeability, resistance to mass tranfer is small, improves extraction efficiency, due to forcing down, passing with column
The advantages that matter speed is fastly and easily modified, reusable, is more and more applied, relative to filled-type extraction column
For, cumbersome filling process is not only eliminated using integral post, and distinctive through hole is the flowing of liquid in integral post
Big hole path is provided, with convective mass transfer instead of slow diffusion mass transfer, so that resistance to mass tranfer is obviously reduced, thus is conducive to
The raising of extraction efficiency.According to the nature difference of object, pass through the design and selection of monomer, the mode of monolithic column solid phase extraction
Hydrophobic (reverse phase) effect, ion exchange, affinity interaction and hydrophilic interaction etc. can be divided into.
1998, polyalcohol integral pole was used for by the Frechet study group [1] of Univ California-Berkeley for the first time
Solid Phase Extraction.By optimizing the ratio of reactant, the extraction efficiency of object is improved.Since then, integral post is led in Solid Phase Extraction
Domain is widely used.Eisert etc.[2] devise the device of In-tube SPME Yu efficient liquid phase on-line coupling；Huang etc.[3]It opens
Sent out a kind of novel Polymer monolith microextraction (PMME) device, with PMME-LC-MS combination determine honey, milk and
The medicament residue of chloramphenicol in egg；Nie etc.[4]By SPME in Organic Polymer Monolithic Columns introduction tube and HPLC on-line coupling skill
In art, in capillary, using toluene, lauryl alcohol as pore-foaming agent, cause free-radical polymerized methacrylic acid-vinyl-dimethyl with heat
Base acrylate, is prepared for capillary monolithic column；Baryla etc.[5]Poly- first is prepared for light initiation polymerization at capillary inlet end
Base acrylate integral post, and it is used for on-line preconcentration inderal；Wang etc.[6]Utilize 2- methyl -2- 2-hydroxyethyl acrylate
Phosphate (HEMA) is monomer and pentaerythritol triacrylate (PETA) is that crosslinking agent preparation poly (PETA-co-HEMA) is whole
Scapus, for the detection to the fluoquinolone substance in egg, the sulfanilamide (SN) substance in milk.From use above it is found that
Line purifies integral post based on preparing in capillary, and the loading capacity and voltage endurance capability of this integral post are poor, type
Also based on reverse phase absorption, the on-line solid phase extraction integral post applied to high-pressure liquid phase system with ion exchange is still
Blank.
Sample after enrichment purification is directly eluted to separation system by on-line solid phase extraction purification techniques, is effectively simplified
Pre-treatment operating procedure avoids sample loss in offline pre-treatment operation and suffers contaminated risk, saves manpower, reduce examination
Agent consumption, the detection method automated at present is applied more and more in detection field.
Summary of the invention
Object of the present invention is to develop a kind of reusable in-line purification integral post, before overcoming existing food residue to analyze
Processing step is various, is difficult to the shortcomings that automating, and provides a kind of sample-pretreating method of simple, quick and high automation.Especially
It refers to that in stainless steel chromatographic column be function monomer, methacrylic acid second two with dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA)
Alcohol ester (EDMA) is crosslinking agent, prepares anion exchange integral post and preparation method thereof by the method for in-situ polymerization.
The present invention establishes simple and rapid food using the series integral post as in-line purification Solid Phase Extraction integral post
The remaining analysis detection new method of acid agrichemical in (such as vegetable and fruit).Integral post selectivity is high, enrichment purification significant effect,
And it is reusable.
Technical solution of the present invention:
A kind of preparation method of anion exchange in-line purification Solid Phase Extraction integral post, includes the following steps:
(1) with dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) for monomer, methacrylic acid glycol ester (EDMA) is to hand over
Join agent, normal propyl alcohol and PEG-400 are pore-foaming agent, and azodiisobutyronitrile (AIBN) is initiator；
(2) based on reactant total volume 1.25mL~2.0mL, 3.7%~6.1% (volume basis of monomer DMAEMA is taken
Than), crosslinking agent EDMA16.7%~20.0% (percent by volume), pore-foaming agent 70%~80% (percent by volume) is added,
AIBN10mg, ultrasonic mixing, degassing；
(3) liquid that step (2) are uniformly mixed is poured into the stainless steel tube of one end sealing, it is then again that the other end is close
Envelope；55 DEG C of water-bath -65 DEG C of reactions 20-30 hours, obtain poly (DMAEMA-co-EDMA) integral post；
(4) finally the integral post that step (3) synthesize is connected on high-pressure pump, washes away pore-foaming agent and unreacted with methanol
The integral post is made, for use in monomer.
Poly (DMAEMA-co-EDMA) integral post can be used for the residue detection analysis of acid agrichemical in vegetable and fruit.
The advantages and positive effects of the present invention:
1, anion exchange in-line purification integral post produced by the present invention is by dimethylaminoethyl acrylate methyl ammonia ethyl ester and methyl
Acrylic acid glycol ester is copolymerized, and the amino that dimethylaminoethyl acrylate methyl ammonia ethyl ester has provides and acidity for polymer backbone
The site of organic matter interaction, and skeleton itself is there is also hydrophobic effect, can selective enrichment purification with carboxyl
Organic compound.
2, the preparation method of the integral post is simple, has continuous poriferous structure, and a large amount of hole is convenient for the outflow of mobile phase,
It is higher than traditional filling extraction efficiency, column back-pressure is low so that resistance to mass tranfer is obviously reduced.
3, the integral post in-situ polymerization can tolerate certain pressure in the chromatographic column of stainless steel, can access well online net
Change enrichment system, realizes the automation of Solid phase extraction step.
4, the integral post property is stable, bio-compatibility is good, can reuse, is selective good, tests prove that, it can answer
In-line purification for acid agrichemical is analyzed.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of whole column section of the invention；
Fig. 2 is the Liquid Chromatography-Tandem Mass Spectrometry figure for implementing acid agrichemical in analysis detection food.I.e. blank apple sample adds
The multiple-reaction monitoring chromatogram added, analyte is 2-methyl-4-chlorophenoxy acetic acid in figure, 2,4,5-T, fluroxypramide, and haloxyfop, trifluoro carboxylic grass
Ether and bispyribac-sodium.
Fig. 3 is the Liquid Chromatography-Tandem Mass Spectrometry figure for implementing acid herbicide in analysis detection food.That is blank bean sprouts sample
The multiple-reaction monitoring chromatogram of addition, analyte is 4-chlorophenoxyacetic acid in figure, 1- methyl α-naphthyl acetate, 2,4-D and gibberellin.
Specific embodiment
Below by specific embodiment, the following further describes the technical solution of the present invention.
The preparation method of embodiment 1:ploy (DMAEMA-co-EDMA) integral post
(1) based on reactant total volume (1.25mL), 3.7% monomer DMAEMA, crosslinking agent 20%EDMA, pore-foaming agent
70%, initiator azodiisobutyronitrile 10mg.Ultrasonic mixing, degassing 30min at room temperature.
(2) by infusion into dry stainless steel void column pipe (10mm × 2.1mm i.d.), both ends sealing, fixed water
55 DEG C of reaction time of bath temperature are the preparation that 30h carries out integral post.And integral post after the reaction was completed is linked into efficient liquid phase
Chromatography high-pressure pump rinses the integral post with methanol to remove unreacted monomer and pore-foaming agent, obtains poly (DMAEMA-co-
EDMA) integral post, for use.
The preparation method of embodiment 2:ploy (DMAEMA-co-EDMA) integral post
(1) based on reactant total volume (2.0mL), 6.1% monomer DMAEMA, crosslinking agent EDMA17%, pore-foaming agent 80%,
Initiator azodiisobutyronitrile 10mg.Ultrasonic mixing, degassing 30min at room temperature.
(2) solution is poured into stainless steel tube after, both ends sealing, 65 DEG C of reaction time of fixed bath temperature are 20h
Carry out the preparation of integral post.And integral post after the reaction was completed is linked into high performance liquid chromatography high-pressure pump, being rinsed with methanol should
Integral post obtains poly (DMAEMA-co-EDMA) integral post to remove unreacted monomer and pore-foaming agent, for use.
Embodiment 3: the integral post prepared using embodiment 1 is spe medium, in conjunction with Liquid Chromatography-Tandem Mass Spectrometry in fruit 5
Kind acid agrichemical carries out in-line purification enrichment detection
1 sample treatment
Fresh pears, apple sample about 10.0g are accurately weighed, are placed in 50mL centrifuge tube, acetonitrile 10mL, anhydrous sodium chloride is added
5g, 15000rpm homogeneous 1min, are centrifuged 5min under the conditions of 5000rpm, take supernatant in 50mL centrifuge tube.Repeat above-mentioned mention
It takes process twice, merges supernatant, take 1mL supernatant, it is to be measured through 0.22 μm of filtering with microporous membrane.
2 test conditions
2.1 in-line purification conditions
On-line solid phase extraction condition is divided into 4 parts: loading, elution, elution and conditioning.
A) loading: it is 5mmol/L ammonium acetate solution that loading, which pumps mobile phase A, and B is acetonitrile, and C is acetone/acetonitrile/isopropanol
(volume ratio 1:1:1), D are 1.5% formic acid-acetonitrile.Experiment using 5mmol/L ammonium acetate solution as loading mobile phase,
Sample volume is 50 μ L.Sample passes through poly (DMAEMA-co-EDMA) on-line solid phase extraction column, and target analytes are retained in purification
On column.
B) it elutes: a part of impurity in matrix being rinsed using acetonitrile and is discharged into waste liquid, while to ensure targeted
Object is closed to remain on solid-phase extraction column.
C) it elutes: during elution, using 1.5% formic acid-acetonitrile as elution mobile phase, target compound being washed
It is de-, and be transferred in analytical column by six-way valve and carry out separation analysis.
D) conditioning: last condition is divided into two parts: the flushing and balance of on-line solid phase extraction column, experimental equilibrium stream
It is dynamic mutually consistent with loading flowing, meanwhile, elution pump driving analysis mobile phase completes the separation of target compound on analytical column.
Chromatographic isolation part uses Agilent Eclipse Plus C18Column (150mm × 4.6mm, 5 μm) is analytical column,
Analysis mobile phase E is acetonitrile, the ammonia spirit that mobile phase F is 0.002%.Wherein eluent gradient changes during in-line purification
Every step uses transient mode, and the variation of the every step of chromatographic separation process is in addition to step 4, step 5, step 6 use gradual-change mode in table 1
Conversion between other steps is all made of transient mode change.In-line purification process is shown in Table 1.
1. in-line purification Liquid Chromatography-Tandem Mass Spectrometry of table measures the eluent gradient elution program of 6 kinds of acid agrichemicals
aIn-line purification: (A) 5mmol/L ammonium acetate solution (B) acetonitrile (C) acetone/acetonitrile/isopropanol (volume ratio 1:
1:1), (D)
1.5% formic acid-acetonitrile solution
bSeparation: the ammonia spirit of (E) acetonitrile (F) 0.002%.
2.2 Mass Spectrometry Conditions
Electric spray ion source；Multiple-reaction monitoring (Multiple reaction monitoring, MRM) anion scans mould
Formula；Sheath atmospheric pressure, 40unit；Assist gas pressure power, 30unit；Ion source temperature: 300 DEG C；Electron spray voltage (Electrospray
Ionization, ESI): 2500V；Surface-induced dissociation voltage (Surface-induced dissociation, SID): 10V；
Capillary temperature: 350 DEG C；Q1, Q3Unit resolution rate: Q1=0.7u, Q3=0.7u；Other determination conditions are shown in Table 2.
Retention time, parent ion, daughter ion and the cracking energy of 2. 6 kinds of acid agrichemicals of table
Note: * quota ion.
3 experimental results
To bispyribac-sodium and haloxyfop, method linear relationship within the scope of 0.1-20ng/mL is good, to 2,4,5-T,
MCPA, acifluorfen and fluroxypramide, method linear relationship within the scope of 0.2-50ng/mL is good, and linearly dependent coefficient r is big
In 0.997.Detection limit and quantitative limit of 6 kinds of acid agrichemicals in apple and pears are 0.2-0.4 and 0.7-1.3 μ g/kg respectively,
Detection limit and quantitative limit in cucumber are 0.4-0.8 and 1.3-2.5 μ g/kg respectively.
The recovery of standard addition that is in a few days averaged of 6 kinds of acid agrichemicals is in 80.6%-115% in food, in a few days relative standard deviation
For 5.1%-13.5%.In the daytime recovery of standard addition is averaged in 79.8%-113%, and relative standard deviation is 5.6%- in the daytime
13.8%.
Under the same conditions, same root poly (DMAEMA-co-EDMA) integral post is after reusing 500 times, back pressure
And the equal no significant difference of extraction efficiency (RSD=7.3%).Existed using the integral post that different batches synthesize to acid agrichemical in food
Line purifies pre-treatment, does not find there is apparent difference on chromatographic column column pressure, appearance situation and extraction efficiency in use,
RSD is calculated with bispyribac-sodium extraction quantity, poly (DMAEMA-co-EDMA) integral post that same batch and different batches synthesize is to double
The RSD of careless ether extraction efficiency is respectively 8.7% and 11.6%.As a result illustrate that the integral post has good mechanical strength, stabilization
Property and reproducibility.
Embodiment 4: using embodiment 2 prepare integral post be spe medium in bean sprouts plant growth regulator it is online only
Change detection
1 sample treatment
Bean sprouts is rubbed after mixing, 5.0g is accurately weighed and is placed in 50mL centrifuge tube, 10mL acetonitrile is added, 5g is anhydrous
Sodium chloride, in 15000rpm homogeneous 1min.It is centrifuged 5min under the conditions of extracting solution 5000rpm, takes supernatant in 50mL centrifuge tube.
It repeats said extracted process twice, merges supernatant, take 1mL supernatant through 0.22 μm of filtering with microporous membrane, it is to be measured.
2 test conditions
2.1 in-line purification
3. in-line purification Liquid Chromatography-Tandem Mass Spectrometry of table measures the eluent gradient elution program of 4 plant growth regulators
aIn-line purification: (A) 5mmol/L ammonium acetate solution (B) acetonitrile (C) acetone/acetonitrile/isopropanol (volume ratio 1:
1:1), (D) 1.5%
Formic acid-acetonitrile solution
bSeparation: the ammonia spirit of (E) acetonitrile (F) 0.002%.
2.2 Mass Spectrometry Conditions
Electric spray ion source；Multiple-reaction monitoring (Multiple reaction monitoring, MRM) anion scans mould
Formula；Sheath atmospheric pressure, 40unit；Assist gas pressure power, 30unit；Ion source temperature: 250 DEG C；Electron spray voltage (Electrospray
Ionization, ESI): 2500V；Surface-induced dissociation voltage (Source-induced dissociation, SID): 10V；
Capillary temperature: 350 DEG C；Q1, Q3Unit resolution rate: 0.7u.Other determination conditions are shown in Table 4.
4 LC-MS/MS of table analyzes retention time, parent ion, daughter ion and the cracking energy of plant growth regulator
* quota ion.
3 experimental results
By bean sprouts mark-on sample analysis, the detection of 4-chlorophenoxyacetic acid is limited to 1.0 μ g/kg, is quantitatively limited to 3.5 μ g/kg,
Gibberellin and 2, the detection of 2 kinds of growth regulators of 4- dichlorphenoxyacetic acid are limited to 1.5 μ g/kg, are quantitatively limited to 5 μ g/kg；1- naphthalene second
The detection of acid is limited to 2.5 μ g/kg, is quantitatively limited to 8.5 μ g/kg, is fully able to meet China, the U.S., Japan and other countries to 4 kinds of lifes
The measurement requirement of the maximum residue limit of long regulator defined.The average recovery of standard addition of 4 kinds of growth regulators exists in bean sprouts
75.0%-93.3%, in a few days relative standard deviation is 4.5%-9.1%, and relative standard deviation is 5.6%-10.2% in the daytime.
Bibliography
[1]Xie S,Svec F,Frechet JMJ.Porous polymer monoliths:Preparation of
sorbent materials with high-surface areas and controlled surface chemistry
for high-throughput,online,solid-phase extraction ofpolar organic compounds
[J].Chem.Mater,1998,10:4072-4078.
[2]Luo YB,Feng Y Q.Stir rod sorpive with monolithic polymer as
coating and its application to the analysis of fluoroquinoloness in honey
sample[J].J.Chromatogr.A.2010,1217:3583-3589.
[3] Wei Yuanlong, Zou Juanjuan, Yang Changlong, Zhang Qinghe, Zhang Weibing, Wang Fengyun, Li Tong polymer Monolithic column
Preparation and condition optimizing [J] chromatography, 2005,23 (4): 251-255.
[4]Hoegger D,Freitag R.Acrylamide-based monoliths as robust
stationary phase for capillary electrochromatography[J].J.Chromatogr.A,2009,
914:211-222.
[5]Hierten S,Mohammad J,Nakazato K.Improment in flow properties and
ph stability of compressed,eontinuous polymer beds for high-performance[J]
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62-79.
Claims (1)
1. a kind of residue detection of anion exchange in-line purification Solid Phase Extraction integral post acid agrichemical in vegetable and fruit is analyzed
Purposes, which is characterized in that the preparation step of the anion exchange in-line purification Solid Phase Extraction integral post is as follows:
(1) with dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA) for monomer, methacrylic acid glycol ester (EDMA) is crosslinking agent,
Normal propyl alcohol and PEG-400 are mixing pore-foaming agent, and azodiisobutyronitrile (AIBN) is initiator；
(2) based on reactant total volume 1.25mL~2.0mL, monomer DMAEMA3.7%~6.1%, crosslinking agent are taken
EDMA16.7%~20.0%, pore-foaming agent 70%~80%, AIBN10mg, ultrasonic mixing, degassing；
(3) liquid that step (2) are uniformly mixed is poured into the stainless steel tube of one end sealing, then again seals the other end；Water
55 DEG C~65 DEG C of bath are reacted 20~30 hours, and poly (DMAEMA-co-EDMA) integral post is obtained；
(4) finally the integral post that step (3) synthesize is connected on high-pressure pump, washes away pore-foaming agent and unreacted list with methanol
The integral post is made, for use in body.
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